Method and composition for inhibition of microbial growth in aqueous food transport and process streams

ABSTRACT

The present invention relates to compositions including peroxyacetic acid and peroxyoctanoic acid and methods for preventing microbial growth in aqueous streams including the step of applying a composition of the invention to the stream. The compositions and methods can control microbial growth in aqueous streams used for transporting or processing food products.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.09/614,631, filed Jul. 12, 2000, which application is incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention relates to compositions including peroxyaceticacid and peroxyoctanoic acid and methods for preventing microbial growthin aqueous streams including the step of applying a composition of theinvention to the stream. The compositions and methods can controlmicrobial growth in aqueous streams used for transporting or processingfood products.

BACKGROUND OF THE INVENTION

One method of handling a large volume of foods, such as, for example,fruits and vegetables, is after selection, to transport these variousfood stuffs by an aqueous medium to transport the food stuffs throughvarious cleaning, handling, and processing steps and environments. Forexample, in specific applications, fresh fruits and vegetables can betransported through water streams by food handling equipment used at aprocessing plant. After picking, fruits and vegetables are introducedinto a flume system wherein water acts as a transport medium and acleaning medium. Water can be used to support and transport the fruitsor vegetables from an unloading site to a final storage or packing orprocessing location. During the transport, water can take a food itemfrom an initial location through a series of somewhat separate stages toa final station where the produce is removed from the water and packed.The water within each stage may carry a varying degree of organic loadin the form of any number of sediments and soluble materials. This wateris generally recycled.

Water can also be used in some of processing stages to further clean,cool, heat, cook, or otherwise modify the food in some fashion prior topackaging. Process water as defined above can sometimes be used once anddiscarded. However, often times a major portion of this process water isre-used and is, therefore, subject to organic and microbialcontamination. In some stages this process water stream is also used totransport the food. In other stages, the process water can be a separatestream and is recycled apart from the transport water. In eithersituation, the process water becomes contaminated with organic matterfrom the food, providing nutrients for microbial growth in the water.

Given the nature of the food as well as the presence of sediments andsoluble materials, the water, flume, and other transport or processingequipment may be subject to the growth of unwanted microorganisms. Waterthat is untreated and recycled during transport or processingaccumulates debris and increased microbial populations. Left untreated,recycled water tends to clean produce early in a shift but contaminatesproduce later in the shift. In fact, flume water has been identified asa potential source of coliform, E. coli and Salmonella contamination orcross contamination during cider production. These and othermicroorganisms are generally undesirable to the food, the water, theflume and can cause buildup on all water contact surfaces of slime orbiofilm, which requires frequent cleaning to remove.

Microbial contamination or cross contamination of fruits and vegetablesvia water continues to be a major concern for produce packers,processors and end users. Although washing fresh produce with water canreduce potential contamination, the wash water can also serve as asource of contamination or cross contamination. If pathogenicmicroorganisms in water are not removed, inactivated or otherwisecontrolled, they can spread to surrounding produce, potentiallycontaminating them. Further, handling or processing steps that pool manyindividual fruits or vegetables tend to increase the risk that a singlecontaminated item may contaminate the entire lot. Immersing orspray-washing fruits and vegetables in fresh water can help reducesurface populations of microorganisms. However sterilization by repeatedwashing, even with sterile water, cannot be achieved becausemicroorganisms within tissues of produce remain in place.

The addition of antimicrobial agents to recycled handling or processwater can inactivate most vegetative cells in water, helping avoid crosscontamination. Ideally, an antimicrobial agent or compound used in sucha system will have several important properties in addition to itsantimicrobial efficacy. The compound or agent should have no residualantimicrobial activity on the food. Residual activity implies thepresence of a film of antimicrobial material which will continue to haveantimicrobial effect which may require further rinsing of the foodproduct. The antimicrobial agent preferably should also be odor free toprevent transfer of undesirable odors onto food stuffs. If direct foodcontact occurs, the antimicrobial agent should also be composed of foodadditive materials which will not effect food if contamination occurs,nor affect humans should incidental ingestion result. In addition, theantimicrobial agent should preferably be composed of naturally occurringor innocuous ingredients, which are chemically compatible with theenvironment and cause no concerns for toxic residues within the water.

In the past, transport and process water apparatus have generally beentreated with sodium hypochlorite and chlorine dioxide. Generally, thesematerials are effective in preventing the unwanted growth ofmicroorganisms. However, the use rate of these chlorine-basedantimicrobials is very high because they tend to be rapidly consumed bythe high organic load included in both the fruits or vegetables andsoil. Further, upon consumption, compounds such as chlorine dioxidedecompose producing byproducts such as chlorites and chlorates, whilehypochlorite produces trichloromethanes which may be toxic in very lowconcentrations. Lastly, chlorine dioxide is a toxic gas with anacceptable air concentration limit of 0.1 ppm. Exposure to ClO₂ oftenleads to headaches, nausea, and respiratory problems, requiringexpensive and intricate safety devices and equipment when it is used.

Further, the efficacy of these common antimicrobial agents on thesurface of fruits and vegetables is often limited. For example, someworkers have reported that chlorine dioxide effectively controlledmicrobial build-up in the cucumber hydrocooling water but had littleeffect on microorganisms on or in the fruit. Other workers showed thatchlorine treatment had little effect on surface microflora of tomatoesand oranges during a packing operation. Another group concluded thatcommonly used antimicrobial agents have only minor effects and shouldnot be relied upon to eliminate microorganisms from produce. Washing rawproduce with chlorinated water is effective in reducing the microbialload, as long as the proper amount of residual chlorine is maintained.

An antimicrobial agent being used more commonly in fresh producetransport or process water is peroxyacetic acid. The EPA approved aperoxyacetic acid-based composition in 1996 for controlling microbialgrowth and reducing biofilm formation in fruit and vegetable transportor process waters. From a historical perspective, peroxyacetic acid hasbeen used for food contact surface sanitizing, aseptic packaging andmedical device cold-sterilization, among other things. In addition toits biocidal properties, the environmentally-friendly decompositionbyproducts and good stability in the presence of vegetable debris helpedgain acceptance of this technology among fruit and vegetable packers,handlers, and processors.

Nevertheless, there remains a need for improved antimicrobialcompositions for treating waters used for transporting or processingfruits or vegetables.

SUMMARY OF THE INVENTION

The present invention relates to compositions including peroxyaceticacid and peroxyoctanoic acid and methods for preventing microbial growthin aqueous streams including the step of applying a composition of theinvention to or as the stream. The aqueous stream can be used fortransporting or processing a food or plant product.

The compositions and methods of the invention are unexpectedly effectivein preventing the growth of unwanted microorganisms in food transportand processing apparatus and on food and plant products. Thecompositions and methods of the invention provide an antimicrobial agentuseful in water for transporting or processing food products which has ahigh degree of antimicrobial efficacy and which is safely ingestible byhumans while imposing no unacceptable environmental incompatibility.

A preferred antimicrobial composition of the present invention includesacetic acid, octanoic acid, peroxyacetic acid, and peroxyoctanoic acid.A preferred composition preferably includes a combination ofperoxyacetic acid and peroxyoctanoic acid effective for killing one ormore of Escherichia coli O157:H7, Listeria monocytogenes, Salmonellajaviana, yeast, and mold. In a preferred embodiment, the concentratecomposition is diluted into flume water employed for transporting orprocessing fruits and/or vegetables.

In one embodiment, an antimicrobial concentrate composition of thepresent invention includes about 50 to about 60 weight-% acetic acid,about 10 to about 20 weight-% octanoic acid, and about 5 to about 15weight-% hydrogen peroxide. In another embodiment, the antimicrobialconcentrate composition of the present invention includes an equilibriummixture resulting from a combination of about 50 to about 60 weight-%acetic acid, about 10 to about 20 weight-% octanoic acid, and about 5 toabout 15 weight-% hydrogen peroxide. In a third embodiment, theantimicrobial concentrate composition of the present invention includesabout 35 to about 45 weight-% acetic acid, about 5 to about 15 weight-%octanoic acid, about 3 to about 8 weight-% hydrogen peroxide, about 8 toabout 16 weight-% peroxyacetic acid, and about 1 to about 5 weight-%peroxyoctanoic acid.

In one embodiment, an antimicrobial use composition of the inventionincludes about 10 to about 150 ppm acetic acid, about 5 to about 40 ppmoctanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 toabout 50 ppm peroxyacetic acid, and about 2 to about 25 ppmperoxyoctanoic acid.

The compositions of the invention can be employed in methods forcontrolling microbial growth in an aqueous stream used for transportingor processing food products. These methods include treating the aqueousstream with a concentrate composition of the invention or employing ause composition of the invention for the aqueous stream.

The compositions can include peroxyseptanoic and/or peroxynonanoic acidin place of or in addition to peroxyoctanoic acid.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates reduction of pathogens on the surface of fruits andvegetables by a peroxyacetic acid/peroxyoctanoic acid mixture of thepresent invention.

FIG. 2 illustrates reduced cross contamination by pathogens when fruitor vegetable handling water includes a peroxyacetic acid/peroxyoctanoicacid mixture of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, a processed fruit or vegetable refers to a fruit orvegetable that has been cut, chopped, sliced, peeled, ground, milled,irradiated, frozen, cooked (e.g., blanched, pasteurized), orhomogenized. As used herein a fruit or vegetable that has been washed,colored, waxed, hydro-cooled, refrigerated, shelled, or had leaves,stems or husks removed is not processed.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat, poultry, fruits and vegetables. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the phrase “plant product” includes any plant substanceor plant-derived substance that might require treatment with anantimicrobial agent or composition. Plant products include seeds, nuts,nut meats, cut flowers, plants or crops grown or stored in a greenhouse,house plants, and the like.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. Whether or notmodified by the term “about”, the claims include equivalents to thequantities.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can effect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed bacteriocidal and thelater, bacteriostatic. A sanitizer and a disinfectant are, bydefinition, agents which provide antibacterial or bacteriocidalactivity. In contrast, a preservative is generally described as aninhibitor or bacteriostatic composition.

Composition of Carboxylic Acids and Peroxycarboxylic Acids

Among other constituents, the composition of the present inventionincludes a carboxylic acid. Generally, carboxylic acids have the formulaR—COOH wherein the R can represent any number of different groupsincluding aliphatic groups, alicyclic groups, aromatic groups,heterocyclic groups, all of which can be saturated or unsaturated aswell as substituted or unsubstituted. Carboxylic acids also occur havingone, two, three, or more carboxyl groups.

Peroxycarboxylic (or percarboxylic) acids generally have the formulaR(CO₃H)_(n), where R is an alkyl, arylalkyl, cycloalkyl, aromatic orheterocyclic group, and n is one, two, or three, and named by prefixingthe parent acid with peroxy. While peroxycarboxylic acids are not verystable, their stability generally increases with increasing molecularweight. Thermal decomposition of these acids can generally proceed byfree radical and nonradical paths, by photodecomposition orradical-induced decomposition, or by the action of metal ions orcomplexes. Percarboxylic acids can be made by the direct, acid catalyzedequilibrium action of 30-98 wt. % hydrogen peroxide with the carboxylicacid, by autoxidation of aldehydes, or from acid chlorides, andhydrides, or carboxylic anhydrides with hydrogen or sodium peroxide.

Typically the compositions and methods of the present invention includeperoxyacetic acid. Peroxyacetic (or peracetic) acid is a peroxycarboxylic acid having the formula: CH₃COOOH. Generally, peroxyaceticacid is a liquid having an acrid odor at higher concentrations and isfreely soluble in water, alcohol, ether, and sulfuric acid. Peroxyaceticacid can be prepared through any number of methods known to those ofskill in the art including preparation from acetaldehyde and oxygen inthe presence of cobalt acetate. A solution of peroxyacetic acid can beobtained by combining acetic acid with hydrogen peroxide. A 50% solutionof peroxyacetic acid can be obtained by combining acetic anhydride,hydrogen peroxide and sulfuric acid. Other methods of formulation ofperoxyacetic acid include those disclosed in U.S. Pat. No. 2,833,813,which is incorporated herein by reference.

Typically the compositions and methods of the present invention includeperoxyoctanoic acid, peroxynonanoic acid, or peroxyseptanoic acid,preferably peroxyoctanoic acid. Peroxyoctanoic (or peroctanoic) acid isa peroxycarboxylic acid having the formula, for example, ofn-peroxyoctanoic acid: CH₃(CH₂)₆OOOH. Peroxyoctanoic acid can be an acidwith a straight chain alkyl moiety, an acid with a branched alkylmoiety, or a mixture thereof. Peroxyoctanoic acid can be preparedthrough any number of methods known to those of skill in the art. Asolution of peroxyoctanoic acid can be obtained by combining octanoicacid and hydrogen peroxide.

A preferred antimicrobial composition of the present invention includesacetic acid, octanoic acid, peroxyacetic acid, and peroxyoctanoic acid.Such a composition can also include a chelating agent. A preferredcomposition preferably includes a combination of peroxyacetic acid andperoxyoctanoic acid effective for killing one or more of Escherichiacoli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, andmold. For example, the composition can kill such microbes on the surfaceof a fruit or vegetable, in water used for transport or processing ofthe fruit or vegetable, and can reduce or prevent transfer of a microbefrom one piece of fruit or vegetable to another (cross contamination).The preferred compositions include concentrate compositions and usecompositions. Typically, an antimicrobial concentrate composition can bediluted, for example with water, to form an antimicrobial usecomposition. In a preferred embodiment, the concentrate composition isdiluted into flume water employed for transporting or processingprocessed or non-processed fruits and/or vegetables.

A preferred antimicrobial concentrate composition of the presentinvention includes about 50 to about 60 weight-% acetic acid, about 10to about 20 weight-% octanoic acid, about 5 to about 15 weight-%hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.Preferably, such an antimicrobial concentrate composition includes about54 weight-% acetic acid, about 10 weight-% hydrogen peroxide, about 0.6weight-% chelating agent, and about 14 weight-% octanoic acid. Thisconcentrate composition can be prepared according to the proportionsdescribed above. After combining the ingredients in these proportions,certain ingredients, such as the acetic acid, octanoic acid, andhydrogen peroxide, react to form peroxyacetic acid and peroxyoctanoicacid.

By about two weeks after combining, the reaction of these ingredientshas approached equilibrium. That is, the relative amounts of one or moreof peroxyacetic acid, acetic acid, peroxyoctanoic acid, octanoic acid,and hydrogen peroxide will be roughly constant. The equilibrium amountwill be affected by decomposition or other reaction, if any, of anylabile species. A preferred antimicrobial concentrate composition of thepresent invention includes an equilibrium mixture resulting from acombination of about 50 to about 60 weight-% acetic acid, about 10 toabout 20 weight-% octanoic acid, about 5 to about 15 weight-% hydrogenperoxide, and about 0.3 to about 1 weight-% chelating agent. A morepreferred antimicrobial concentrate composition of the present inventionincludes an equilibrium mixture resulting from a combination of about 54weight-% acetic acid, about 14 weight-% octanoic acid, about 10 weight-%hydrogen peroxide, and about 0.6 weight-% chelating agent.

A preferred antimicrobial concentrate composition of the presentinvention includes about 35 to about 45 weight-% acetic acid, about 5 toabout 15 weight-% octanoic acid, about 3 to about 8 weight-% hydrogenperoxide, about 8 to about 16 weight-% peroxyacetic acid, about 1 toabout 5 weight-% peroxyoctanoic acid, and about 0.1 to about 2 weight-%chelating agent. Preferably, such an antimicrobial concentratecomposition includes about 40 weight-% acetic acid, about 10 weight-%octanoic acid, about 5 weight-% hydrogen peroxide, about 12 weight-%peroxyacetic acid, about 3 weight-% peroxyoctanoic acid, and about 0.6weight-% chelating agent. These preferred compositions can be producedby mixing the acid and peroxide components at proportions listed inpreceding paragraphs and allowing the composition to sit at ambienttemperature for a period of approximately two weeks. That is, thesepreferred compositions can be considered equilibrium compositions.

The compositions of the present invention also include antimicrobial usecompositions. Preferred antimicrobial use compositions include about 10to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid,about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppmperoxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, andabout 0.2 to about 2.5 ppm chelating agent. Preferably, such anantimicrobial use composition about 133 ppm acetic acid, about 33 ppmoctanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyaceticacid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.Different dilutions of a concentrate composition can result in differentlevels of the components of the use composition, generally maintainingthe relative proportions. For example, a use composition of the presentinvention can have concentrations twice, one half, or one quarter thoselisted above.

The level of reactive species, such as peroxy acids and/or hydrogenperoxide, in a use composition can be affected, typically diminished, byorganic matter that is found in or added to the use composition. Forexample, when the use composition is a flume transporting fruits orvegetables, fruit or vegetable organic matter or accompanying organicmatter will consume peroxy acid and peroxide. Thus, the present amountsof ingredients in the use compositions refer to the composition beforeor early in use, with the understanding that the amounts will diminishas organic matter is added to the use composition.

In each of the compositions described above, the chelating agent is anoptional, but preferred, ingredient. Typically the balance of each ofthe compositions described above is made up primarily or exclusively ofa solvent, such as water, e.g. tap or other potable water.

The compositions of the present invention preferably include onlyingredients that can be employed in food products or in food transport,handling, or processing, for example, according to government (e.g. FDAor EPA) rules and regulations. In addition, the present compositions arepreferably free of a coupling agent. Preferably, the composition is freeof any peroxycarboxylic acid or carboxylic acid with 10 or more carbonatoms. Such 10 or more carbon acids can impart undesirable residues(e.g. bad tasting and/or malodorous) to a fruit or vegetable.

As used herein, a composition or combination “consisting essentially” ofcertain ingredients refers to a composition including those ingredientsand lacking any ingredient that materially affects the basic and novelcharacteristics of the composition or method. The phrase “consistingessentially of” excludes from the claimed compositions and methods: acoupling agent; an ingredient that cannot be employed in food productsor in food transport, handling, or processing according to U.S.government rules or regulations; and/or a peroxycarboxylic acid orcarboxylic acid with 10 or more carbon atoms; unless such an ingredientis specifically listed after the phrase.

Each of the compositions listed above can be formulated by combiningeach of the listed ingredients. In addition, certain compositionsincluding both acid and peroxy acid can be formulated by combining theacids and hydrogen peroxide, which forms peroxy acids. Typically, the pHof an equilibrium mixture is about 1, and the pH of a 10% solution ofthe equilibrium mixture in water is about 2.4.

Hydrogen Peroxide

The antimicrobial composition of the invention typically also include ahydrogen peroxide constituent. Hydrogen peroxide in combination with thepercarboxylic acid provides a surprising level of antimicrobial actionagainst microorganisms despite the presence of high loadings of organicsediment. Additionally, hydrogen peroxide can provide an effervescentaction which can irrigate any surface to which it is applied. Hydrogenperoxide works with a mechanical flushing action once applied whichfurther cleans the surface of application. An additional advantage ofhydrogen peroxide is the food compatibility of this composition upon useand decomposition. For example, combinations of peroxyacetic acid andhydrogen peroxide result in acetic acid, water, and oxygen upondecomposition all of which are food product compatible.

While many oxidizing agents can be used, hydrogen peroxide is generallypreferred for a number of reasons. After application of theH₂O₂/peroxyacetic acid germicidal agent, the residue left merelyincludes water and an acidic constituent. Deposition of these productson the surface of an apparatus, such as a flume, will not adverselyeffect the apparatus, the handling or processing, or the food productstransported therein.

Hydrogen peroxide (H₂O₂), has a molecular weight of 34.014 and it is aweakly acidic, clear, colorless liquid. The four atoms are covalentlybonded in a H—O—O—H structure. Generally, hydrogen peroxide has amelting point of −0.41° C., a boiling point of 150.2° C., a density at25° C. of 1.4425 grams per cm³, and a viscosity of 1.245 centipoise at20° C.

Adjuvants

The antimicrobial composition of the invention can also include anynumber of adjuvants. Specifically, the composition of the invention caninclude stabilizing agents, wetting agents, as well as pigments or dyesamong any number of constituents which can be added to the composition.

Stabilizing agents can be added to the composition of the invention tostabilize the peracid and hydrogen peroxide and prevent the prematureoxidation of this constituent within the composition of the invention.Chelating agents or sequestrants generally useful as stabilizing agentsin the present compositions include alkyl diamine polyacetic acid-typechelating agents such as EDTA (ethylene diamine tetraacetate tetrasodiumsalt), acrylic and polyacrylic acid-type stabilizing agents, phosphonicacid, and phosphonate-type chelating agents among others. Preferablesequestrants include phosphonic acids and phosphonate salts including1-hydroxy ethyldene-1,1-diphosphonic acid (CH₃C(PO₃H₂)₂OH),amino[tri(methylene phosphonic acid)] ([CH₂PO₃H₂]₂(ethylenediamine[tetra methylene-phosphonic acid)], 2-phosphenebutane-1,2,4-tricarboxylic acid, as well as the alkyl metal salts,ammonium salts, or alkyloyl amine salts, such as mono, di, ortetra-ethanolamine salts. The stabilizing agent is used in aconcentration ranging from about 0 weight percent to about 20 weightpercent of the composition, preferably from about 0.1 weight percent toabout 10 weight percent of the composition, and most preferably fromabout 0.2 weight percent to 5 weight percent of the composition.

Also useful in the composition of the invention are wetting anddefoaming agents. Wetting agents function to increase the penetrationactivity of the antimicrobial composition of the invention. Wettingagents which can be used in the composition of the invention include anyof those constituents known within the art to raise the surface activityof the composition of the invention.

Along these lines surfactants, and especially nonionic surfactants, canalso be useful in the present invention. Nonionic surfactants which canbe useful in the present invention are those which include ethyleneoxide moieties, propylene oxide moieties, as well a mixtures thereof,and ethylene oxide-propylene oxide moieties in either heteric or blockformation. Additionally useful in the present invention are nonionicsurfactants which include an alkyl ethylene oxide compounds, alkylpropylene oxide compounds, as well as mixtures thereof, and alkylethylene oxide-propylene oxide compounds where the ethylene oxidepropylene oxide moiety is either in heteric or block formation. Furtheruseful in the present invention are nonionic surfactants having anymixture or combination of ethylene oxide-propylene oxide moieties linkedto a alkyl chain where the ethylene oxide and propylene oxide moietiescan be in any randomized or ordered pattern and of any specific length.Nonionic surfactants useful in the present invention can also includerandomized sections of block and heteric ethylene oxide propylene oxide,or ethylene oxide-propylene oxide.

Generally, the concentration of nonionic surfactant used in acomposition of the present invention can range from about 0 wt-% toabout 5 wt-% of the composition, preferably from about 0 wt-% to about 2wt-% of the concentrate composition, and most preferably from about 0wt-% to about 1 wt-% of the composition.

The composition used in the methods of the invention can also containadditional ingredients as necessary to assist in defoaming.

Generally, defoamers which can be used in accordance with the inventioninclude silica and silicones; aliphatic acids or esters; alcohols;sulfates or sulfonates; amines or amides; halogenated compounds such asfluorochlorohydrocarbons; vegetable oils, waxes, mineral oils as well astheir sulfated derivatives; fatty acid soaps such as alkali, alkalineearth metal soaps; and phosphates and phosphate esters such as alkyl andalkaline diphosphates, and tributyl phosphates among others; andmixtures thereof.

Especially preferable, are those antifoaming agents or defoamers whichare of food grade quality given the application of the method of theinvention. To this end, one of the more effective antifoaming agentsincludes silicones. Silicones such as dimethyl silicone, glycolpolysiloxane, methylphenol polysiloxane, trialkyl or tetralkyl silanes,hydrophobic silica defoamers and mixtures thereof can all be used indefoaming applications. Commercial defoamers commonly available includesilicones such as Ardefoam® from Armour Industrial Chemical Companywhich is a silicone bound in an organic emulsion; Foam Kill® or Kresseo®available from Krusable Chemical Company which are silicone andnon-silicone type defoamers as well as silicone esters; and Anti-Foam A®and DC-200 from Dow Corning Corporation which are both food grade typesilicones among others. These defoamers can be present at aconcentration range from about 0.01 wt-% to 5 wt-%, preferably fromabout 0.01 wt-% to 2 wt-%, and most preferably from about 0.01 wt-% toabout 1 wt-%.

The composition of the invention can also contain any number of otherconstituents as necessitated by the application, which are known tothose of skill in the art and which can facilitate the activity of thepresent invention. Preferably, the compositions of the present inventionare free of a coupling agent.

Methods Employing the Compositions of the Invention

The concentrate and use compositions of the present invention can beemployed for a variety of antimicrobial purposes, preferably as or forforming water-based systems for processing and/or transporting processedor unprocessed fruits or vegetables. Preferred methods of the presentinvention include employing a composition of the invention in a recycledwater system, such as a washing, transport, or processing flume. Theadvantageous stability of the present compositions in such methods whichinclude the presence of fruit or vegetable debris makes thesecompositions competitive with cheaper, less stable, and potentiallytoxic chlorinated compounds. Preferred methods employing the presentcompositions include fruit or vegetable flumes. Conventional fruit orvegetable flume methods employ a sodium/calcium hypochloriteantimicrobial, and the present compositions are an advantageoussubstitute in these methods. Preferred methods of the present inventioninclude agitation of the use composition, particularly as a concentrateis added to water to make a use composition. Preferred methods includerecycled water systems that have some agitation.

The present methods require a certain minimal contact time of thecomposition with a microbe for occurrence of antimicrobial activity. Thecontact time can vary with the type of fruit or vegetable, quality ofthe fruit or vegetable, amount of soil on the fruit or vegetable, numberof microorganisms on the fruit or vegetable, temperature of the usecomposition, or the like. Preferably the exposure time is a least about60 seconds. The amount of reduction of microbial organisms can varyaccording to the conditions of use such as: concentration of peroxy acidin the use composition, temperature, exposure time, and the fruit orvegetable surface.

Methods of the invention include applying the present compositions to afood product, a plant product, produce, or a plant. For example, acomposition of the invention can be applied to a plant in a green houseto remove microbes from or to prevent microbes from establishingthemselves on the plant. By way of further example, a composition of theinvention can be applied to poultry parts during processing and beforepackaging to reduce the microbial load on the poultry.

The present invention may be better understood with reference to thefollowing examples. These examples are intended to be representative ofspecific embodiments of the invention, and are not intended as limitingthe scope of the invention.

EXAMPLES Example 1 Formulas for Peroxyacetic/Peroxyoctanoic AcidMixtures Having Activity Against Microbes Contaminating Fruits andVegetables

A preferred antimicrobial concentrate composition of the invention wasformulated as:

Raw Material Weight % Glacial Acetic Acid 54 Hydrogen Peroxide, 35% 30HEDP, 60% 1 Octanoic Acid, 95% 15

This concentrate formulation converted to a composition including peroxyacids during storage for two weeks at generally ambient conditions. Inthis case, the concentrate composition converted to:

Typical Weight Percent of Chemical In Concentrate Chemical 2 WeeksPost-Manufacture Acetic Acid 40% Hydrogen Peroxide  5% HEDP 0.6% Octanoic Acid 10% Peroxyacetic Acid 12% Peroxyoctanoic Acid  3%The remainder of this concentrate composition was water.

The equilibrated concentrate composition was diluted for use to atypical maximum level of peroxyacetic acid of 40 ppm, and an overallformulation of:

Typical Weight ppm of Chemical in Use- Chemical Solution 2 WeeksPost-Manufacture Acetic Acid 133 ppm  H₂O₂ 17 ppm HEDP  2 ppm OctanoicAcid 33 ppm Peroxyacetic Acid 40 ppm Peroxyoctanoic Acid 10 ppmThe remainder of this use composition was water.

Example 2 Antimicrobial Efficacy of a Peroxyacetic/Peroxyoctanoic AcidMixture Against Microbes Isolated from Fruits or Vegetables

This study compared antimicrobial efficacy of a peroxyaceticacid/peroxyoctanoic acid mixture to peroxyacetic acid alone forapplication in fruit or vegetable transport or process waters. Thisstudy measured the antifungal potency of both chemistries in aqueoussystems through laboratory rate-of-kill testing employing fungiharvested from fresh produce.

Materials and Methods Preparation of Fungi for Rate of Kill Testing

Routine transfer to Sabouraud Dextrose agar slants maintained culturesof Candida parapsilosis (from blueberry processing water), Rhodotorulaspecies (from celery processing water), Cryptococcus species (frompotato processing water) and Zygosaccharomyces bailii (ATCC 60483).Growth was harvested by adding 5 mL of phosphate buffered water to theslant, mixing and then transferring the suspension into 90 mL ofphosphate buffered water. The resulting suspension was used for testing.

Routine transfer to Sabouraud Dextrose agar slants maintained culturesof Aspergillus species (from onion processing water), Penicilliumspecies (from celery processing water) and Cladosporium species (frompotato processing water). Conidia suspensions of each mold were preparedby subculturing each mold to Sabouraud Dextrose agar plates andincubating until thick aerial mycelia with conidia were evident. Conidiawere harvested by adding approximately 10 mL of phosphate buffered waterto the plate, scraping the mycelia and collecting the suspension in aflask. The suspension was filtered through sterile gauze to remove largemycelia fragments from the conidia. The resulting suspension was usedfor testing.

Preparation of Antimicrobial Agents for Rate of Kill Testing

Two antimicrobial agents were used for testing. The first agentcontained peroxyacetic acid. The second contained a peroxyaceticacid/peroxyoctanoic acid mixture. Both agents were diluted in steriledeionized water to achieve a total peracid concentration of 80 ppm. Thecomposition of the use-solutions were as follows:

Peroxyacetic Peroxyacetic/Peroxyoctanoic Chemical Acid Agent Acid AgentPeroxyacetic Acid 80 ppm 64 ppm Octanoic Acid None 53 ppm PeroxyoctanoicAcid None 16 ppm

Measuring Rate of Fungus Kill

The rate at which peroxyacetic acid and a peroxyaceticacid/peroxyoctanoic acid mixture killed fungi was measured byinoculating use-solutions of each antimicrobial agent with fungi andthen quantifying survivors after various exposure times.

Testing was performed in duplicate. 99 mL of each antimicrobialuse-solution was transferred to a 250 mL Erlenmeyer flask and allowed toequilibrate to 25° C. The liquid in the flask was swirled vigorously ina rapid circular motion and 1 mL of a fungus suspension was added. After30 seconds, 2, 5 or 10 minutes 1 mL quantities of the use-solution weretransferred to 9 mL of an inactivating solution including 0.1% sodiumthiosulfate. 1 mL quantities of the inactivating solution werepour-plated using Sabouraud Dextrose agar. Serial 100-fold dilutions ofthe inactivating solution were also plated. Agar plates were incubatedfor 72 hours at 26° C. before counting survivors. The log reduction offungi due to the antimicrobial agent was determined by comparingreduction to a water control.

Results Rate of Fungus Kill

The starting populations of Candida parapsdosis, Rhodotorula sp.,Cryptococcus sp. and Zygosaccharomyces bailii in suspension were 7.30,4.88, 8.08 and 5.98 Log₁₀ CFU/mL respectively. Cryptococcus sp. was themost susceptible to both peracid agents (Table 1). The osmophilic yeastZygosaccharomyces bailii was the least susceptible. The peroxyaceticacid/peroxyoctanoic acid mixture reduced the number of yeast cells insuspension faster than the peroxyacetic acid agent.

TABLE 1 Average log reduction of yeast by peroxyacetic acid (POAA) and aperoxyacetic/peroxyoctanoic acid (POAA/POOA) mixture. 30 Seconds 2Minutes 5 Minutes POAA/ POAA/ POAA/ POAA POOA POAA POOA POAA POOACandida 0.34 3.49 1.49 3.46 3.42 4.12 parapsilosisRhodotorula >3.88 >3.88 >3.88 >3.88 >3.88 >3.88 sp.Cryptococcus >7.08 >7.08 >7.08 >7.08 >7.08 >7.08 sp. Z. bailii 0.16 0.420.18 4.32 0.94 4.80

The starting populations of Aspergillus sp., Penicillium sp. andCladosporium sp. were 6.28, 6.45 and 5.18 Log₁₀ CFU/mL respectively.Cladosporium sp. was the most susceptible to both peracid agents (Table2). Aspergillus sp. was the least susceptible. The peroxyaceticacid/peroxyoctanoic acid mixture reduced the number of mold conidia insuspension faster than the peroxyacetic acid agent.

TABLE 2 Average log reduction of mold by peroxyacetic acid (POAA) and aperoxyacetic/peroxyoctanoic acid (POAA/POOA) mixture. 2 Minutes 5Minutes 10 Minutes POAA/ POAA/ POAA/ POAA POOA POAA POOA POAA POOAAspergillus sp. 0 0.13 0 1.60 0 2.13 Penicillium sp. 0 4.19 0.45 4.791.52 5.45 Cladosporium 1.86 >4.18 4.18 >4.18 >4.18 >4.18 sp.

These results can also be expressed as improvements in the kill rate(Table 3). A peroxyacetic/peroxyoctanoic acid mixture typicallydemonstrates greater kill rate against bacteria, yeast & mold thanperoxyacetic acid when diluted to the same concentration of peracid.Improvements in the kill rate are illustrated in Table 3. Kill rate ofspoilage yeast and mold kill in suspension is substantially improved:

TABLE 3 Improvement in spoilage fungi kill rate by aperoxyacetic/peroxyoctanoic acid mixture of the present invention.Improvement in Reduction^(a) Fungus 30 sec. 2 min. 5 min. 10 min.Candida parapsilosis (yeast) +3.15 Log +1.97 Log +0.70 Log —Zygosaccharomyces bailii (yeast) +0.26 Log +4.14 Log +3.86 Log —Aspergillus sp. (mold) — +0.13 Log +1.60 Log +2.13 Log Penicillium sp.(mold) — +4.19 Log +4.34 Log +3.93 Log Fusarium sp. (mold) — — +3.04 Log+2.30 Log Cladosporium sp. (mold) — +2.32 Log   0 Log   0 Log^(a)Improvement in Reduction = (POAA/POOA Log(reduction) − POAA Log(reduction))

Discussion

The predominant microorganisms on fruits or vegetables are mesophilicand psychrotrophic gram-negative bacteria, most commonly Pseudomonas,Enterobacter and Erwinia species. Coliform bacteria, lactic acidbacteria and fungi typically make up the balance of the total microbepopulation. During transport or processing, these microorganisms end-upin the recycled wash water and can multiply and grow to high numbers ifleft unchecked. Because of this, antimicrobial agents used in fruit orvegetable transport or process water should at a minimum control theproliferation of gram-negative bacteria. Without this control, transportor process water quickly becomes a vector for cross-contamination. Themore that organisms are reduced the better the preventive action.

Peroxyacetic acid has a history of potency against vegetative bacteria.It provided consistent control of these organisms in this study,including coliform bacteria. The peroxyacetic/peroxyoctanoic acidmixture showed greater antibacterial activity than peroxyacetic acid byitself against bacteria at the same total peracid concentration. Anotherof the peroxyacetic/peroxyoctanoic acid mixture's strengths appears tobe as a broader spectrum and more potent fungicide than peroxyaceticacid.

Conclusions

Testing in laboratory aqueous systems indicated that theperoxyacetic/peroxyoctanoic acid mixture had broader spectrum, morepotent antifungal efficacy than peroxyacetic acid. Theperoxyacetic/peroxyoctanoic acid mixture provided a better antimicrobialefficacy profile for treatment of fruit or vegetable transport orprocess water.

Example 3 Antimicrobial Efficacy of a Peroxyacetic/Peroxyoctanoic AcidMixture in Fruit or Vegetable Transport and Process Waters

This study compared antimicrobial efficacy of a peroxyaceticacid/peroxyoctanoic acid mixture to peroxyacetic acid alone forapplication in fruit or vegetable transport and process waters. Thisstudy was performed during actual vegetable processing served toevaluate microbial counts in wash water and on fresh-cut vegetablesexposed to peracid-treated waters.

Materials and Methods Concentration of Antimicrobial Agents in Fresh-CutVegetable Processing Water

Vegetable processing water testing was done using the same antimicrobialagents as in laboratory aqueous system testing. The varyingconcentrations of each agent are listed in the results section.Municipal tap water was the diluent.

Antimicrobial Efficacy in Vegetable Processing Water

The reduction of microorganisms in vegetable processing water treatedwith peroxyacetic acid or a peroxyacetic acid/peroxyoctanoic acidmixture was determined. Testing was done in two separate recycled watersystems. In both systems, cut vegetables fell into a water stream thatcarried them to a de-watering area where they were collected for furtherprocessing. The water that the vegetables traveled in was routed to abalance tank that fed back into the original water stream thuscompleting the process loop. One system was used to wash cut, raw celeryor cabbage. The other system was used to transport cut, raw potatoes toa blancher.

During processing of each vegetable, 10 water samples were collected insterile plastic bags containing an inactivating agent (0.01% sodiumthiosulfate). 1 mL quantities were plated on Petrifilm® (3M, Inc.)Aerobic Plate Count, Coliform Count and Yeast & Mold Count media.Validation of these media using this procedure was performed prior toinitiating testing (data not presented). Serial 100-fold dilutions werealso plated. Petrifilms were incubated at 35° C. for 24 hours (ColiformCount), 35° C. for 48 hours (Aerobic Plate Count), or at roomtemperature for 72 hours (Yeast & Mold Count). The number ofmicroorganisms was counted following incubation.

Antimicrobial Efficacy on Fresh-Cut Vegetables

Microorganism reduction on vegetable surfaces in the transport andprocess water was determined while water analyses were being conducted.Ten samples of each cut vegetable were collected just prior to fallinginto the process water stream and just after de-watering.

Eleven grams of each sample were transferred to bag containing 99 mL ofsterile phosphate buffered water. Contents of the bag were mixed in aStomacher brand mixer for approximately 1 minute. Afterwards, 1 mL ofthe mixture was plated on Petrifilm brand Aerobic Plate Count, ColiformCount and Yeast & Mold Count media. 1 mL quantities of 100-fold serialdilutions were also plated. Petrifilms were incubated and enumerated asdescribed above in this Example.

Statistical Analyses

A single-factor analysis of variance (ANOVA) using Microsoft Excelsoftware was used to determine if microorganism numbers in transport andprocess water treated with the peroxyacetic acid/peroxyoctanoic mixturewere significantly lower than those with peroxyacetic acid. At an alphalevel of 0.05, if results showed that P 0.05, a significant lowering wasconcluded. The same analysis was used to evaluate the significance ofreduction on vegetable surfaces.

Results Antimicrobial Efficacy in Fresh-Cut Vegetable Processing Water

The concentration of total peracid in the celery and cabbage processingwater was approximately the same for both chemicals. The concentrationof total peracid from the peroxyacetic acid agent in the potato processwater was approximately 20 ppm greater than the total peracidconcentration from the peroxyacetic/peroxyoctanoic acid mixture. Boththe peroxyacetic and peroxyacetic/peroxyoctanoic acid mixture reducedthe number of coliform bacteria to levels undetected by the testprotocol (Table 4). The celery process water treated with theperoxyacetic/peroxyoctanoic acid mixture showed significantly lowernumbers of total aerobic bacteria than peroxyacetic acid treated water(P≦0.05). No significant difference in total bacteria numbers wasobserved in cabbage or potato water. All process waters treated with theperoxyacetic/peroxyoctanoic acid mixture showed significantly lowernumbers of yeast and mold than peroxyacetic acid treated water (P≦0.05).

TABLE 4 Average number (log CFU/mL) of microorganisms in fresh-cutvegetable process water containing peroxyacetic acid (POAA) or aperoxyacetic/peroxyoctanoic acid (POAA/POOA) mixture. Aerobic Yeast &Plate Count Coliform Count Mold Count POAA/ POAA/ POAA/ POAA POOA POAAPOOA POAA POOA Celery^(a) 2.02 1.21 0 0 1.86 0.32 Cabbage^(b) 1.92 1.780 0 2.02 0.97 Potatoes^(c) 0.92 0.95 0 0 5.48 2.67 ^(a)Averageconcentration of peracid from POAA agent = 38 ppm, from POAA/POOA agent= 39 ppm. ^(b)Average concentration of peracid from POAA agent = 26 ppm,from POAA/POOA agent = 29 ppm. ^(c)Average concentration of peracid fromPOAA agent = 54 ppm, from POAA/POOA agent = 32 ppm.

Antimicrobial Efficacy on Fresh-Cut Vegetables

The peroxyacetic/peroxyoctanoic acid mixture showed significantlygreater reductions of coliform bacteria on celery and yeast and mold onpotatoes than peroxyacetic acid (P≦0.05) (Table 5).

TABLE 5 Average log reduction of microorganisms on fresh-cut vegetablesafter 30 second exposure to process water containing peroxyacetic acid(POAA) or a peroxyacetic/peroxyoctanoic acid (POAA/POOA) mixture.Aerobic Bacteria Coliform Bacteria Yeast & Mold Reduction ReductionReduction POAA/ POAA/ POAA/ POAA POOA POAA POOA POAA POOA Celery^(a)1.07 1.09 0.77 1.41 0.68 0.96 Cabbage^(b) 0.84 0.85 >0.88 >0.23 0.770.82 Potatoes^(c) 1.54 1.59 >1.58 >1.66 No reduc- No reduc- tion, counttion, count increase increase of 2.87 of 0.83 ^(a)Average concentrationof peracid from POAA agent = 38 ppm, from POAA/POOA agent = 39 ppm.^(b)Average concentration of peracid from POAA agent = 26 ppm, fromPOAA/POOA agent = 29 ppm. ^(c)Average concentration of peracid from POAAagent = 54 ppm, from POAA/POOA agent = 32 ppm.

Discussion

The predominant microorganisms on fresh-cut fruits or vegetables and inthe water used to wash them are mesophilic and psychrotrophicgram-negative bacteria, most commonly Pseudomonas, Enterobacter andErwinia species. Coliform bacteria, lactic acid bacteria and fungitypically make up the balance of the total microbial population. Duringtransport or processing, these microorganisms end-up in the recycledwash water and can multiply and grow to high numbers if left unchecked.Because of this, antimicrobial agents used in fruit or vegetabletransport or process water should at a minimum control the proliferationof gram-negative bacteria. Without this control, transport or processwater quickly becomes a vector for cross-contamination. The more thatorganisms are reduced the better the preventive action.

Peroxyacetic acid has a history of potency against vegetative bacteria.It provided consistent control of these organisms in this study,including coliform bacteria. The peroxyacetic/peroxyoctanoic acidmixture showed greater antibacterial activity than peroxyacetic acid byitself against bacteria at the same total peracid concentration.However, one of the peroxyacetic/peroxyoctanoic acid mixture's strengthsappears to be as a broader spectrum and more potent fungicide thanperoxyacetic acid. It substantially reduced yeast and mold numbers intransport and process water, which led to less funguscross-contamination depositing on fresh-cut fruit or vegetable surfaces.

Conclusions

Under actual processing conditions, the peroxyacetic/peroxyoctanoic acidmixture showed greater antibacterial activity than peroxyacetic acid. Italso substantially reduced yeast and mold numbers in transport andprocess water, leading to less fungus cross-contamination depositing onfresh-cut fruit or vegetable surfaces. The peroxyacetic/peroxyoctanoicacid mixture provided a better antimicrobial efficacy profile fortreatment of fresh-cut fruit or vegetable process water.

Example 4 Peroxyacetic/Peroxyoctanoic Acid Mixtures Exhibit SuperiorActivity Against Pathogenic Bacteria

Historical data on chlorine and sodium/calcium hypochlorite indicatesthat these chemicals have antimicrobial properties. Because of theseproperties, they are used in fruit and vegetable transport or processwater to reduce microbial contamination. Unlike chlorinated competitors,the present peroxyacetic/peroxyoctanoic acid mixtures offer advantageousantimicrobial efficacy against pathogenic bacteria.

Materials and Methods

The following procedure was employed for determining whether acomposition killed pathogenic bacteria (e.g. Escherichia coli O157:H7,Listeria monocytogenes, or Salmonella javiana) on the surface of a fruitor vegetable. Bacteria were applied to tomato surfaces and allowed a 1-2hour attachment time. Contaminated tomatoes were submersed in aperoxyacetic/peroxyoctanoic acid mixture according to the presentinvention (at a level yielding 40 ppm peroxyacetic acid) or water for 1minute without agitation. After 1 minute, tomatoes were transferred to asolution that neutralized the peroxy acids and peroxides and massagedfor 3 minutes to remove attached bacteria. The number of attachedbacteria that survived treatment was determined using standard agarplating technique. The number of bacteria that “fell off” the tomatointo the water or peroxyacetic/peroxyoctanoic acid mixture according tothe present invention, and survived, was also determined byneutralization and agar plating technique. A similar experiment wasconducted employing a peroxyacetic acid antimicrobial composition.

The following procedure was employed for testing the ability of acomposition to reduce the number of pathogenic bacteria (e.g.Escherichia coli O157:H7, Listeria monocytogenes, or Salmonella javiana)on the surface of fruits and vegetables that occurred throughcross-contamination. Bacteria were applied to cherry tomato surfaces andallowed a 24-hour attachment time. The inoculated tomatoes, along withsome non-inoculated tomatoes, were submersed in aperoxyacetic/peroxyoctanoic acid mixture according to the presentinvention (at a level yielding 40 ppm peroxyacetic acid) or water for 1minute with agitation. After 1 minute, non-inoculated tomatoes wereremoved and transferred to a solution that neutralized the peroxy acidsand peroxides. The neutralizing solution was vortex mixed for 45 secondsto remove cross-contaminated bacteria. The number of cross-contaminatedbacteria that survived treatment was determined using standard agarplating technique.

Results

A peroxyacetic/peroxyoctanoic acid mixture according to the presentinvention significantly lowered the numbers of all three bacteria ontomato surfaces (FIG. 1). It also reduced the numbers all three bacteriasuspended in solution by >99% compared to water. This mixture alsosignificantly lowered the number of cross-contaminated bacteria ontomato surfaces compared to water (FIG. 2).

A peroxyacetic acid composition (lacking peroxyoctanoic acid) causedreductions in pathogenic bacteria that were smaller than those achievedwith the peroxyacetic/peroxyoctanoic acid mixture. For example, 20 ppmPOAA produced only a 57% reduction in the E. coli O157:H7 in tomato washwater; at 40 ppm the reduction was 88%, and at 60 ppm the reduction was94%. For L. monocytogenes on tomatoes, POAA produced a reduction of 84%at 20 ppm, of 95% at 40 ppm, and of 98% at 60 ppm. At 20 and 40 ppm,POAA produced no reduction in amounts of S. javiana, but at 60 ppm thereduction was 91%.

Discussion

It is possible to reduce the numbers of pathogenic bacteria on producesurfaces through cleansing action alone, for example, submersingbroccoli in a soap-based solution. The problem with this reductionmethod is that bacteria removed from the surface may remain viable andtransfer to other food or equipment surfaces. This transfer of bacteriais known as cross-contamination. Fortunately, mixtures of the presentinvention reduced the numbers of Escherichia coli O157:H7, Listeriamonocytogenes, and Salmonella javiana on fruit and vegetable surfacesthat occurred through cross-contamination. These reductions weresuperior to those produced by much larger amounts of peroxyacetic acid.

Conclusions

The compositions of the present invention reduced the numbers ofEscherichia coli O157:H7, Listeria monocytogenes and Salmonella javianaon fruit and vegetable surfaces through bactericidal activity, and alsoreduced cross-contamination. Reducing through bactericidal/killingactivity versus physical removal is one advantage of the presentcompositions.

Example 5 A Peroxyacetic/Peroxyoctanoic Acid Mixture has No AdverseEffect on Appearance of Fruits or Vegetables

Certain antimicrobial agents, such as high levels of chlorine, can haveadverse effects on the appearance of fresh cut fruits or vegetables.This example demonstrates that a peroxyacetic/peroxyoctanoic acidmixture of the present invention has no adverse effect on the appearanceof fresh-cut fruits or vegetables.

Materials and Methods

The effect of a peroxyacetic/peroxyoctanoic acid mixture of the presentinvention on vegetable appearance was studied. Processed vegetables wereexposed to water, chlorinated water, and water containing aperoxyacetic/peroxyoctanoic acid mixture of the present invention, whichhad the same formula as the mixtures employed in Examples 2 and 3.Vegetables were then spun to remove excess moisture, packaged in sealedplastic bags and refrigerated. Appearance was noted daily for 1 week andthe results are reported in Table 6, below.

Results

Processed vegetables treated with water containing aperoxyacetic/peroxyoctanoic acid mixture of the present invention didnot appear any different than those treated with water or a low level ofchlorine (Table 6).

TABLE 6 Appearance of refrigerated processed vegetables over 1 weekafter a 10 minute submersion in water, sodium hypochlorite or aperoxyacetic/peroxyoctanoic acid mixture of the present invention.Vegetable Appearance Over 1 Week at 40° F. Sodium HypochloritePeroxyacetic/Peroxyoctanoic (40 ppm available Acid mixture (40 ppmVegetable chlorine, pH 6.5) peroxyacetic acid) Chopped Lettuce Same aswater treated Same as water treated Shredded Carrots Same as watertreated Same as water treated Chopped Onions Same as water treated Sameas water treated Chopped Celery Same as water treated Same as watertreated Diced Tomatoes Same as water treated Same as water treatedSliced Potatoes Same as water treated Same as water treated Cut GreenBeans Same as water treated Same as water treated Chopped Cabbage Sameas water treated Same as water treated Cut Sweet Corn Same as watertreated Same as water treated

Discussion

Appearance changes are the result of spoilage mechanisms. Spoilagedevelopment usually coincides with growth of microorganisms, but thisdoes not necessarily mean that all spoilage is of microbial origin. Infact, the events that usually begin spoilage in a processing environmentare physical damage and normal enzymatic reactions. Microbialdegradation usually occurs as a result of these two events. Chlorine isstill used as an antimicrobial agent in wash water for produce. Highdosages (200-300 ppm) are often used to meet the chlorine demand oflarge wash systems. It is believed that such high chlorine levels cancause adverse discoloration and leave off-flavors in fresh processedproduce.

Conclusions

Accelerated spoilage is usually the result of physical injury andenzymatic oxidation that leads to microbial degradation—not poormicroorganism removal during washing. The high levels of chlorinesometimes needed for washing can cause discoloration or off-flavors onprocessed fruits or vegetables. Processed fruits or vegetables treatedwith water containing a peroxyacetic/peroxyoctanoic acid mixture of thepresent invention did not appear any different than those treated withwater or low levels of chlorine.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains.

The invention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications may be made while remainingwithin the spirit and scope of the invention.

We claim:
 1. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 35 to about 45 weight-% acetic acid, about 5 to about 15 weight-% octanoic acid, about 3 to about 8 weight-% hydrogen peroxide, about 8 to about 16 weight-% peroxyacetic acid, about 1 to about 5 weight-% peroxyoctanoic acid, and about 0.1 to about 2 weight-% chelating agent.
 2. The antimicrobial concentrate composition of claim 1, comprising about 40 weight-% acetic acid, about 10 weight-% octanoic acid, about 5 weight-% hydrogen peroxide, about 12 weight-% peroxyacetic acid, about 3 weight-% peroxyoctanoic acid, and about 0.6 weight-% chelating agent.
 3. An antimicrobial use composition comprising: a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 4. The antimicrobial use composition of claim 3, comprising about 133 ppm acetic acid, about 33 ppm octanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyacetic acid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.
 5. The antimicrobial use composition of claim 3, wherein an aqueous flume comprises the composition.
 6. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising an equilibrium mixture resulting from a composition of about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% octanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 7. The antimicrobial concentrate composition of claim 6, comprising an equilibrium mixture resulting from a composition of about 54 weight-% acetic acid, about 14 weight-% octanoic acid, about 10 weight-% hydrogen peroxide, and about 0.6 weight-% chelating agent.
 8. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% octanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 9. The antimicrobial concentrate composition of claim 8, comprising about 54 weight-% acetic acid, about 10 weight-% hydrogen peroxide, about 0.6 weight-% chelating agent, and about 14 weight-% octanoic acid.
 10. An antimicrobial use composition comprising: food product and a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 11. The antimicrobial use composition of claim 11, comprising the food product, about 133 ppm acetic acid, about 33 ppm octanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyacetic acid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.
 12. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: treating the aqueous stream with a combination of peroxyacetic acid and peroxyoctanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable.
 13. The method of claim 12, wherein the combination comprises about 35 to about 45 weight-% acetic acid, about 5 to about 15 weight-% octanoic acid, about 3 to about 8 weight-% hydrogen peroxide, about 8 to about 16 weight-% peroxyacetic acid, about 1 to about 5 weight-% peroxyoctanoic acid, and about 0.1 to about 2 weight-% chelating agent.
 14. The method of claim 13, wherein the combination comprises about 40 weight-% acetic acid, about 10 weight-% octanoic acid, about 5 weight-% hydrogen peroxide, about 12 weight-% peroxyacetic acid, about 3 weight-% peroxyoctanoic acid, and about 0.6 weight-% chelating agent.
 15. The method of claim 12, wherein treating produces the aqueous stream comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 16. The method of claim 15, wherein treating produces the aqueous stream comprising about 133 ppm acetic acid, about 33 ppm octanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyacetic acid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.
 17. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: administering an antimicrobial concentrate composition to the stream, the antimicrobial concentrate composition comprising an equilibrium mixture resulting from a composition of about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% octanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 18. The method of claim 17, comprising administering to the stream an equilibrium mixture resulting from a composition of about 54 weight-% acetic acid, about 14 weight-% octanoic acid, about 10 weight-% hydrogen peroxide, and about 0.6 weight-% chelating agent.
 19. The method of claim 17, wherein administering produces the aqueous stream comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 20. The method of claim 19, wherein administering produces the aqueous stream comprising about 133 ppm acetic acid, about 33 ppm octanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyacetic acid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.
 21. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: producing the aqueous stream comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm octanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyoctanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 22. The method of claim 21, wherein the aqueous stream comprises about 133 ppm acetic acid, about 33 ppm octanoic acid, about 17 ppm hydrogen peroxide, about 40 ppm peroxyacetic acid, about 33 ppm peroxyoctanoic acid, and about 2 ppm chelating agent.
 23. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 35 to about 45 weight-% acetic acid, about 5 to about 15 weight-% septanoic or nonanoic acid, about 3 to about 8 weight-% hydrogen peroxide, about 8 to about 16 weight-% peroxyacetic acid, about 1 to about 5 weight-% peroxyseptanoic or peroxynonanoic acid, and about 0.1 to about 2 weight-% chelating agent.
 24. An antimicrobial use composition comprising: a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm septanoic or nonanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyseptanoic or peroxynonanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 25. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising an equilibrium mixture resulting from a composition of about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% septanoic or nonanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 26. An antimicrobial concentrate composition comprising: a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% septanoic or nonanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 27. An antimicrobial use composition comprising: food product and a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable; the combination comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm septanoic or nonanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyseptanoic or peroxynonanoic acid, and about 0.2 to about 2.5 ppm chelating agent.
 28. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: treating the aqueous stream with a combination of peroxyacetic acid and peroxyseptanoic or peroxynonanoic acid effective for killing Escherichia coli O157:H7, Listeria monocytogenes, Salmonella javiana, yeast, and mold on the surface of a fruit or vegetable.
 29. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: administering an antimicrobial concentrate composition to the stream, the antimicrobial concentrate composition comprising an equilibrium mixture resulting from a composition of about 50 to about 60 weight-% acetic acid, about 10 to about 20 weight-% septanoic or nonanoic acid, about 5 to about 15 weight-% hydrogen peroxide, and about 0.3 to about 1 weight-% chelating agent.
 30. A method of controlling microbial growth in an aqueous stream used for transporting or processing food product, the method comprising: producing the aqueous stream comprising about 10 to about 150 ppm acetic acid, about 5 to about 40 ppm septanoic or nonanoic acid, about 4 to about 20 ppm hydrogen peroxide, about 5 to about 50 ppm peroxyacetic acid, about 2 to about 25 ppm peroxyseptanoic or peroxynonanoic acid, and about 0.2 to about 2.5 ppm chelating agent. 